EP0448056A2 - Méthode de préparation de matières luminescentes contenant des sulfures - Google Patents

Méthode de préparation de matières luminescentes contenant des sulfures Download PDF

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Publication number
EP0448056A2
EP0448056A2 EP91104258A EP91104258A EP0448056A2 EP 0448056 A2 EP0448056 A2 EP 0448056A2 EP 91104258 A EP91104258 A EP 91104258A EP 91104258 A EP91104258 A EP 91104258A EP 0448056 A2 EP0448056 A2 EP 0448056A2
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Prior art keywords
sulfide
phosphor
carbon
preparing
sulfide phosphor
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EP91104258A
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German (de)
English (en)
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EP0448056B1 (fr
EP0448056A3 (en
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Shuji Inaho
Michael Devoe Christiansen
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Mitsubishi Chemical Corp
USR Optonix Inc
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Kasei Optonix Ltd
USR Optonix Inc
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Definitions

  • the present invention has been conducted in view of the above-mentioned situations. Accordingly, it is the object of the present invention to provide a method for preparing a sulfide phosphor of high luminance by industrial mass-production, in which introduction of a toxic gas such as hydrogen sulfide into the firing container from the outward is unnecessary and the atmosphere in the firing container is always kept to be a sulfurizing atmosphere suitable for production of the sulfide phosphor during the step of firing the raw material mixture for the phosphor.
  • a toxic gas such as hydrogen sulfide
  • the inventors of the present invention conducted various investigations to accomplish the above object. Specifically, they studied such materials that could form a sulfurizing gas in the firing container when fired along with the raw material mixture for phosphor for the purpose of maintaining the sulfurizing atmosphere in the inside of the firing container throughout the firing stage (the material of the kind is hereinafter referred to as an "auxiliary material").
  • Figure 1 shows sectional views to outline some embodiments of arrangement of the raw material mixture for phosphor and the auxiliary material in a firing heat-resistant container, which are processed in accordance with the method of the present invention or with the conventional method.
  • Figure 2 shows graphs to illustrate the relations between the amount of the auxiliary material to be employed in the method for preparing the sulfide phosphor of the present invention and the relative brightness of the sulfide phosphor to be obtained and the chromaticity coordinates as expressed by CIE standard chromaticity diagram.
  • a raw material for the matrix such as ZnS or (Zn,Cd)S
  • a raw material for the activator such as a compound of Ag, a compound of Cu or a compound of Au
  • a raw material for the co-activator such as a compound of Al or a compound of Ga
  • the method of the present invention is especially effective for preparing sulfide phosphors containing aluminium (Al) as a co-activator, such as ZnS:Cu,Al phosphor, ZnS;Ag,Al phosphor, ZnS:Au,Cu,Al phosphor or (Zn,Cd)S:Cu,Al phosphor, since aluminium (Al) is easily diffused in the phosphor crystals. Accordingly, Al-containing sulfide phosphors having a higher luminance can be prepared by the method of the present invention, than those prepared by the conventional methods.
  • sulfide phosphors having a halogen such as chlorine (Co), bromine (Br) or iodine (I) as the co-activator may also be prepared by the method of the present invention.
  • a halogen such as chlorine (Co), bromine (Br) or iodine (I) as the co-activator.
  • any improvement of the emission luminance of the phosphors prepared by the method of the present invention could not almost be admitted as compared with the phosphors prepared by the conventional methods.
  • At least one selected from the sulfides of metals of iron (Fe), copper (Cu), zinc (Zn), bismuth (Bi) and antimony (Sb) is especially preferably employed, as giving sulfide phosphors of high emission luminance.
  • sulfides of iron or zinc are most recommended from the practical viewpoints that they do not almost contaminate the phosphors prepared and they are low-prices.
  • the "metal sulfides” may be either definite proportional compounds where the respective metal elements and sulfur are stoichiometrically bonded to form one molecule or indefinite proportional compounds where the respective metal components and sulfur are bonded in any desired proportions.
  • the auxiliary material preferably contains sulfur, in addition to the above-mentioned "carbon” and "metal sulfide".
  • sulfur-containing auxiliary material a part of the sulfur which has gasified at a relatively low temperature in the initial stage of firing could react with the co-existing "metal sulfide" to be trapped as an indefinite proportional compound of "metal sulfide", and the thus trapped compound could also react with the co-existing "carbon” after the middle stage of firing. Accordingly, employment of such sulfur-containing auxiliary material is more effective for continuously maintaining the sulfurizing atmosphere in the inside of the heat-resistant container throughout the step of firing the phosphors.
  • the raw material mixture (2) for the phosphor of a determined amount is filled in the first heat-resistant container (1), and the second heat-resistant container (3) filled with the auxiliary material (4) is put on the raw material mixture (2), and thereafter the container (1) is covered with the lid (5) and fired.
  • the wall of the second heat-resistant container (3) which is to be in contact with the raw material mixture (2) may have numerous gas-permeable small through-holes.
  • the point "0" of ZnS means the conventional method, where an auxiliary material of a mixture comprising sulfur and carbon was filled in the second heat-resistant container, in place of the auxiliary material system composed of ZnS ("metal sulfide") and carbon, in the manner of Figure 1(A) and fired along with the raw material mixture for the phosphor to obtain ZnS:Cu,Al phosphor. That is to say, the point "0" of ZnS indicates the emission luminance and the emitted color from the ZnS:Cu,Al phosphor thus prepared by the conventional method.
  • sulfide phosphors of higher luminance can be prepared more efficiently be the method of the present invention than those to be prepared by the conventional methods without changing the color to be emitted from the sulfide phosphors.
  • the above-mentioned raw materials for a phosphor were weighed, and a small amount of water was added thereto to make a paste. This was kneaded, dried and sieved, and 7 g of sodium chloride (NaCl), 7 g of zinc chloride (ZnCl2) and 3.5 g of sulfur (S) were added thereto and well blended in a ball mill to obtain a raw material mixture for a phosphor. The resulting mixture was then filled in a quartz crucible having a capacity of approximately one liter (the first heat-resistant container).
  • the porcelain crucible (the second heat-resistant container) as filled with the above-mentioned auxiliary material mixture was put on the above-mentioned raw material mixture for a phosphor as filled in the quartz crucible (the first heat-resistant container), and the quartz crucible (the first heat-resistant container) was covered with a lid and was then put in a high-temperature electric furnace kept at 980°C, where the materials in the containers were fired for 2 hours.
  • the thus fired product was then taken out of the furnace and cooled and then washed with water and dried to finally obtain ZnS:Ag,Al phosphor as co-activated by 0.015% of Ag and 0.0075% of Al (Sulfide Phosphor (I)).
  • a comparative sample was prepared. Specifically, the same process as above was repeated, except that a mixture comprising 70 g of sulfur and 18 g of active charcoal was employed as the auxiliary materials to be filled in the porcelain container in place of the mixture comprising 17 g of active charcoal, 70 g of sulfur and 70 g of ZnS, and ZnS:Ag,Al phosphor as co-activated with 0.015% of Ag and 0.0075% of Al (Sulfide Phosphor (I-R)) was prepared.
  • a mixture comprising 70 g of sulfur and 18 g of active charcoal was employed as the auxiliary materials to be filled in the porcelain container in place of the mixture comprising 17 g of active charcoal, 70 g of sulfur and 70 g of ZnS, and ZnS:Ag,Al phosphor as co-activated with 0.015% of Ag and 0.0075% of Al (Sulfide Phosphor (I-R)) was prepared.
  • a comparative sample was prepared in the same manner. Specifically, the same process as above was repeated, except that an auxiliary material mixture comprising 70 g of sulfur and 18 g of active charcoal was put in a porcelain container having a capacity of approximately 150 ml and the container was put on the raw material mixture for the phosphor as filled in the quartz crucible (the first heat-resistant container) as shown in Figure 1(A), in place of employing the auxiliary material mixture comprising 17 g of active charcoal, 70 g of sulfur and 70 g of ZnS as filled in the quartz tube (the second heat-resistant container), and ZnS:Cu,Al phosphor as co-activated with 0.015% of Cu and 0.006% of Al (Sulfide Phosphor (II-R)) was prepared.
  • an auxiliary material mixture comprising 70 g of sulfur and 18 g of active charcoal was put in a porcelain container having a capacity of approximately 150 ml and the container was put on the raw material mixture for the phosphor as filled in the quartz crucible

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Electroluminescent Light Sources (AREA)
EP91104258A 1990-03-21 1991-03-19 Méthode de préparation de matières luminescentes contenant des sulfures Expired - Lifetime EP0448056B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/496,949 US5102579A (en) 1990-03-21 1990-03-21 Method for preparing sulfide phosphors
US496949 1990-03-21

Publications (3)

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EP0448056A2 true EP0448056A2 (fr) 1991-09-25
EP0448056A3 EP0448056A3 (en) 1992-04-01
EP0448056B1 EP0448056B1 (fr) 1995-08-30

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EP (1) EP0448056B1 (fr)
JP (1) JP2957015B2 (fr)
KR (1) KR0175311B1 (fr)
DE (1) DE69112459T2 (fr)

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US6072198A (en) * 1998-09-14 2000-06-06 Planar Systems Inc Electroluminescent alkaline-earth sulfide phosphor thin films with multiple coactivator dopants
US6346326B1 (en) 1998-10-15 2002-02-12 Sarnoff Corporation Coated moisture impervious red phosphors
US6351069B1 (en) 1999-02-18 2002-02-26 Lumileds Lighting, U.S., Llc Red-deficiency-compensating phosphor LED
US6680569B2 (en) 1999-02-18 2004-01-20 Lumileds Lighting U.S. Llc Red-deficiency compensating phosphor light emitting device
US6183102B1 (en) 1999-03-12 2001-02-06 Global Products Sales And Marketing, L.L.C. Apparatus and method for producing a transparent tubular member containing a phosphorescent material
US7173179B2 (en) * 2002-07-16 2007-02-06 The Board Of Trustees Of The University Of Arkansas Solar co-generator
CN1973018A (zh) * 2004-06-24 2007-05-30 住友电气工业株式会社 荧光体、其制备方法及使用该荧光体的粒子分散型el器件
US7847302B2 (en) * 2005-08-26 2010-12-07 Koninklijke Philips Electronics, N.V. Blue LED with phosphor layer for producing white light and different phosphor in outer lens for reducing color temperature
WO2007086311A1 (fr) * 2006-01-27 2007-08-02 Semiconductor Energy Laboratory Co., Ltd. Matériau photoémetteur, élément photoémetteur, dispositif photoémetteur, et appareil électronique
WO2007086310A1 (fr) * 2006-01-27 2007-08-02 Semiconductor Energy Laboratory Co., Ltd. Matériau photoémetteur, dispositif photoémetteur et dispositif électronique
US20070190675A1 (en) * 2006-02-10 2007-08-16 Semiconductor Energy Laboratory Co., Ltd. Manufacturing method of display device
WO2007091500A1 (fr) * 2006-02-10 2007-08-16 Semiconductor Energy Laboratory Co., Ltd. Element emetteur de lumiere, dispositif emetteur de lumiere, et dispositif electronique
US20070190235A1 (en) * 2006-02-10 2007-08-16 Semiconductor Energy Laboratory Co., Ltd. Film forming apparatus, film forming method, and manufacturing method of light emitting element
US20070194321A1 (en) * 2006-02-17 2007-08-23 Semiconductor Energy Laboratory Co., Ltd. Light emitting element, light emitting device, and electronic device
EP1821579A3 (fr) * 2006-02-17 2008-04-02 Semiconductor Energy Laboratory Co., Ltd. Élément électroluminescent, dispositif électroluminescent, et appareil électronique
CN101395966A (zh) * 2006-03-02 2009-03-25 株式会社半导体能源研究所 发光元件、发光设备、照明设备和电子器具
US20070205410A1 (en) * 2006-03-03 2007-09-06 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic device
KR20080110747A (ko) 2006-03-21 2008-12-19 가부시키가이샤 한도오따이 에네루기 켄큐쇼 발광소자, 표시장치 및 전자기기
US20070281574A1 (en) * 2006-06-01 2007-12-06 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing electroluminescent material
US20080012027A1 (en) * 2006-07-13 2008-01-17 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and method of fabricating light-emitting element
CN102892861A (zh) * 2010-05-14 2013-01-23 堺化学工业株式会社 硫化锌蓝色荧光体及其制造方法
JP5763509B2 (ja) * 2011-11-29 2015-08-12 住友金属鉱山株式会社 希土類添加硫化物蛍光体の製造方法

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Also Published As

Publication number Publication date
EP0448056B1 (fr) 1995-08-30
KR0175311B1 (ko) 1999-03-20
EP0448056A3 (en) 1992-04-01
DE69112459D1 (de) 1995-10-05
US5102579A (en) 1992-04-07
JP2957015B2 (ja) 1999-10-04
DE69112459T2 (de) 1996-05-02
JPH06192655A (ja) 1994-07-12

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